EP1470163B1 - Polysaccharide esters and their use as binders in coatings - Google Patents

Polysaccharide esters and their use as binders in coatings Download PDF

Info

Publication number
EP1470163B1
EP1470163B1 EP03704483A EP03704483A EP1470163B1 EP 1470163 B1 EP1470163 B1 EP 1470163B1 EP 03704483 A EP03704483 A EP 03704483A EP 03704483 A EP03704483 A EP 03704483A EP 1470163 B1 EP1470163 B1 EP 1470163B1
Authority
EP
European Patent Office
Prior art keywords
inulin
paint
polyester
drying
pbw
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03704483A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1470163A1 (en
Inventor
Everardus A. p/a Ato Business Unit Oostveen
John Weijnen
Jacco p/a Ato Business Unit Van Haveren
Michel Gillard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sigma Coatings BV
Original Assignee
Sigma Coatings BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sigma Coatings BV filed Critical Sigma Coatings BV
Priority to EP03704483A priority Critical patent/EP1470163B1/en
Publication of EP1470163A1 publication Critical patent/EP1470163A1/en
Application granted granted Critical
Publication of EP1470163B1 publication Critical patent/EP1470163B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0051—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Fructofuranans, e.g. beta-2,6-D-fructofuranan, i.e. levan; Derivatives thereof
    • C08B37/0054—Inulin, i.e. beta-2,1-D-fructofuranan; Derivatives thereof

Definitions

  • the present invention relates to air-drying varnish or paint compositions. More particularly, the present invention relates to polyesters prepared from renewable materials and their use as binders in said air-drying varnish or paint composition. The present invention further relates to methods for the preparation of said polyesters and to air-drying varnish or paint compositions comprising said polyesters.
  • Conventional air-drying paint composition may comprise alkyd oligomers as binders. These alkyds used in coating formulations suitable for application at ambient temperatures are synthesised by a polycondensation reaction of polycarboxylic acids, polyhydric alcohols and unsaturated fatty acids or oils. Highly suitable polycarboxylic acids, are for instance, phthalic acid(anhydride), isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, succinic acid, glutaric acid and tetrahydrophthalic acid(anhydride).
  • phthalic acid(anhydride) isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, succinic acid, glutaric acid and tetrahydrophthalic acid(anhydride).
  • the polyalcohols habitually used in the alkyd synthesis are amongst others: pentaerythritol, dipentaerythritol, glycerol, ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, trimethylol propane, trimethylol ethane, di-trimethylol propane and 1,6 hexane diol.
  • pentaerythritol dipentaerythritol
  • glycerol ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, trimethylol propane, trimethylol ethane, di-trimethylol propane and 1,6 hexane diol.
  • the majority of the aforementioned polyacids and polyalcohols are alkyd building blocks derived from petrochemical feedstocks.
  • modifying components which may be optionally included in the manufacture of air-drying alkyd resins are: isocyanates as toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate, benzoic acid, abietic acid, phenolic resins, siloxanes, and vinyl monomers such as styrene, vinyl toluene alkyl and (meth)acrylates.
  • Glycerol and the diacids, adipic acid, sebacic acid, maleic acid, fumaric acid, succinic acid and glutaric acid and abietic acid are obtainable from renewable sources but led to alkyd paints with insufficient hardness development and low solids content.
  • EP-A-792888 discloses esters of inulin wherein at least one of the inulin hydroxyl groups is esterified with a saturated C 2 -C 22 carboxylic acid, and their use as surface-active substances. Claimed preparation of such esters is by reaction of inulin with: (a) the acid chloride or anhydride using pyridine as the sole solvent; (b) the acid anhydride using water as the sole solvent or using no solvent; or (c) an ester of the acid using a catalyst but no solvent. The same or a mixture of acids can be used to esterify the OH groups, with the degree of substitution (DS) being 1, preferably 0.5.
  • GB-A-2337950 discloses antifouling coating compositions containing a non-drying polysaccharide ester as film-forming binder.
  • WO-A-9422919 discloses the uses of fatty acid esters of polysaccharides as a component of a hot melt adhesive and as a coating for active ingredients such as fertilisers.
  • WO-A-9948946 discloses polyol fatty acid polyesters obtained by reacting unesterified first polyol having hydroxy groups with second polyol esterified with fatty acids, such as triglycerides.
  • the air-drying paint and varnish compositions of the present invention are based on binders that can be prepared from renewable materials. They are characterised in that said binders essentially consist of polyesters that can be obtained by transesterification or interesterification of inulin or an acyl ester thereof, and a drying oil, a semi-drying oil or derived alkyl esters thereof.
  • the present invention also comprises methods for the preparation of said polyesters according to claims 6-11 and to the use of said polyesters as binders in coatings.
  • the invention also comprises said binders and their use in air-drying paint or varnish compositions.
  • acyl refers to an alkyl group attached to a carbon-oxygen double bond. More in particular acyl as used herein refers to a radical of formula R 1 CO- wherein R 1 represents an alkyl.
  • alkyl as-used herein, alone or in combination, means straight and branched chained saturated hydrocarbon radicals containing from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms.
  • examples of such radicals include methyl, ethyl, n-propyl, isopropyl n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl and the like.
  • said acyl ester of inulin is a lower acyl ester, wherein "lower” as used herein refers to C 1-4 carbon atoms.
  • Suitable acyl esters of inulin are acetate ester, propionate ester and the like.
  • said derived alkyl ester of drying or semi-drying oil relates to short chain alkyl ester of fatty acids, wherein "short-chain” as used herein refers to C 1-6 carbon atoms.
  • Suitable short chain alkyl ester of said fatty acids are methyl ester, ethyl ester and the like.
  • the present invention relates to polyesters obtainable by interesterification of (i) an acyl ester of inulin of general formula G(F) n wherein G represents a glucose moiety, F represents a fructose moiety, and n is at least 2, and (ii) a drying oil, a semi-drying oil or derived alkyl esters thereof.
  • the present invention relates to polyesters obtainable by transesterification of (i) inulin of general formula G(F) n wherein G represents a glucose moiety, F represents a fructose moiety, and n is at least 2, and (ii) C 1-6 alkyl ester of unsaturated fatty acids.
  • the polyesters according to the invention may have an average degree of substitution ranging from 0.2 to 3.0 wherein the degree of substitution is the average number of substituted OH functions per monosaccharide unit generally determined using 13 C-NMR. According to another embodiment, the polyester may have a degree of substitution ranging from 0.5 to 2.5 or for example from 1.0 to 2.0.
  • polyesters of the present invention are obtained by transesterification of:
  • Inulin is a polymer of (2->1)- ⁇ -D-fructofuranan with a terminal ⁇ -D-glucopyranosyl group. Inulin is often summarised as G(F) n , wherein G represents a glucose moiety, F represents a fructose moiety, according to an embodiment n varies from 2 to 60. Industrially, inulin is used primarily in the food sector for such purposes as the production of diabetic bread and fructose syrup.
  • Inulin is a very widespread carbohydrate in nature and occurs in composites, such as chicories, Jerusalem artichoke, dahlias and artichokes as well as in other types of plants, in which it serves as a storage material. It is isolated in economically significant amounts from chicory (Cichorium intybus) and Jerusalem artichokes. Depending on the type of plant and on the harvesting time, inulin has different molecular weight distributions and different average chain lengths between 8 and 25. The size of individual molecules ranges, in general, from 5 to 50 monosaccharide units per chain. There are, however, native inulins having an average chain length greater than 25 and correspondingly longer individual chains.
  • Sucrose can also be the raw material for enzymatic production of short chain inulin.
  • the enzyme takes a fructose unit from a sucrose molecule and transfers it to another sucrose molecule to make oligomers such as kestose (GF 2 ), nystose (GF 3 ) fructofuranosyl nystose (GF 4 ).
  • the inulin or the acyl ester thereof selected for use in the preparation of the polyesters according to the invention may have a narrow molecular weight distribution, characterised by a polydispersity of maximum 10.
  • the polydispersity can be lower than 2, or lower than 1.5, preferably lower than 1.3.
  • Polydispersity is defined as the ratio of the weight-average molecular weight to the number-average molecular weight; it is generally determined using size exclusion chromatography (SEC).
  • drying oil, semi-drying oil or derived alkyl esters thereof, used in the preparation of the polyesters according to the invention can be appropriately selected to impart air-drying properties to the binders and hence to the paint or varnish compositions based on said binders.
  • Drying and semi-drying oils are mixtures of saturated, mono, di, tri-unsaturated fatty acids triglycerides, more in particular they are triglycerides of unsaturated long chain carboxylic acids, which have usually at least 10 carbon atoms, typically about 10 to about 24, preferably about 16 to 22 atoms and most preferably about 18 to 20 carbon atoms.
  • semi-drying and drying fatty acids fatty acids that have the same aliphatic chain composition as the oils they are derived from.
  • the classification of the oils is based on the iodine number; for drying oil the iodine number is >140; for semi-drying oil the iodine number is ranging between 125 and 140, and for non-drying oil the iodine number is ⁇ 125 ("Surface Coatings", by Swaraj Paul, John Wiley and Sons; p.89).
  • the unsaturated fatty acids encountered in these drying or semi-drying oils may have an iodine number of at least 100 expressed in terms of the number of centigrams of iodine per gram of fatty acids (e.g. ASTM test method D-1959). According to an embodiment, said fatty acids have an iodine number ranging between 100 and 140. For example, said fatty acids may have an iodine number greater than 125 (semi-drying) or 140 (drying).
  • Typical but non-limiting examples of unsaturated fatty acids useful in the present invention are: safflower fatty acid, tall oil fatty acid, rapeseed oil fatty acid, peanut oil fatty acid, soya bean oil fatty acid, linseed oil fatty acid, sardine oil fatty acid, herring oil fatty acid, tallow oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, and mixtures thereof.
  • Various drying and semi-drying oils and the properties of such oils are reviewed in Surface Coatings", by Swaraj Paul, John Wiley and Sons, incorporated herein by reference.
  • the present invention also relates to method for the preparation of a polyester according to the invention, comprising the steps of transesterification of:
  • the present invention relates to a method for the preparation of a polyester according to the invention comprising the step of interesterification of (i) an acyl ester of inulin of general formula G(F) n wherein G represents a glucose moiety, F represents a fructose moiety and n is at least 2, and (ii) a drying oil, a semi-drying oil or derived alkyl esters thereof.
  • the present invention relates to a method for the preparation of a polyester according to the invention, comprising the step of transesterification of (i) inulin of general formula G(F) n wherein G represents a glucose moiety, F represents a fructose moiety and n is at least 2, and (ii) C 1-6 alkyl ester of unsaturated fatty acids.
  • partial esterification e.g. resins with a degree of substitution less than 3.0
  • the amount of free residual hydroxyl groups can be diminished by an additional reaction with for example acetic anhydride.
  • the inulin may be optionally acylated prior to reaction with a drying oil, or a semi-drying oil or derived alkyl esters thereof.
  • the transesterification or interesterification reaction may be carried out by reacting the inulin or lower acyl ester of inulin and the oil or derived lower alkyl esters at a temperature of 120 to 170 °C for 4 to 24 hours.
  • the interesterification or transesterification reaction may be carried out in the presence of a polar aprotic solvent.
  • said reaction is performed in an inert atmosphere and optionally under reduced pressure.
  • Suitable catalysts for performing said reaction include but are not limited to K 2 CO 3 , Na 2 CO 3 , LiOH and NaOMe.
  • the inulin:oil ratio is adapted to obtain the desired degree of substitution. If needed, hydrogen peroxide can be used to bleach the resulting product at a temperature of 25 to 40°C.
  • the free hydroxyl groups of the polyesters obtained through the transesterification procedure may be acylated by a low molecular weight acid derivative such as acetic anhydride.
  • the polyesters of this invention exhibit a narrow molecular weight distribution.
  • a low polydispersity of the polyester is favourable for a low intrinsic polyester viscosity and consequently only a limited amount of cutting solvent is required to obtain a practical processing viscosity.
  • Typical amounts of organic solvent to dilute the polyester binder are less than about 40 weight %, preferably less than about 15% and more preferably less than about 10%.
  • Suitable organic solvents to dilute the polyester binders of the invention include aliphatic, cycloaliphatic and aromatic hydrocarbons, alcohol ethers, alcohol ether esters and N-methylpyrrolidone. However, it may also be an aqueous carrier containing the polyester in the form of an emulsion and a suitable emulsifier as is well known in the art.
  • An additional advantage of a narrow molecular weight distribution is that after curing a homogeneously cross-linked polymeric network is obtained with improved overall film properties as high elasticity.
  • polyesters of this invention find particular use as binders in coating compositions, especially in high solids coating compositions. More in particular, the polyesters according to the invention can be used as binders in paints and varnishes.
  • the polyesters may be formulated into coating compositions such as varnish or paint.
  • the paints may optionally comprise various pigments, extenders, corrective and constructive additives and liquid carriers.
  • the varnishes may optionally comprise extenders, corrective and constructive additives and liquid carriers.
  • Non-limiting examples of such materials include: inorganic and organic pigments, siccatives, anti-skinning agents, pigment and substrate wetting agents, anti-sagging agents, anti-oxidants, bactericides, fungicides, foam suppressing agents, slip agents, flow and levelling agents, UV-absorbers, HALS-radical scavengers, corrosion inhibitors, waxes, anti-crater additives, organic solvents and water.
  • the present invention further relates to air-drying paint or varnish composition
  • air-drying paint or varnish composition comprising as a binder a polyester according to the invention and at least one drier.
  • the cure process in air-drying involves oxidation, i.e. reaction with oxygen from the air. It is always performed in the presence of a drier, also known as a catalyst, which is usually a combination of metal salts.
  • a drier also known as a catalyst
  • Suitable autoxidation catalysts which are also called driers or siccatives, are carboxylates or alkoxylates of alkali, alkali-earth, transition and rare earth metals.
  • Typical examples are metal salts in which the anion is, for example, naphtenic acid, 2-ethyl-hexanoic acid, neodecanoic acid, decanoic acid, dodecanoic acid, isocarboxylic acid, sebacic and linolenic acid.
  • Cobalt, manganese, iron, lead, zirconium, strontium, aluminium, cerium, vanadium, silver, titanium, calcium, barium, bismuth, zinc, lithium and potassium may be mentioned as suitable metals.
  • mixtures of metal salts are used as for the autoxidation of alkyd resins, where at least one of the metals exhibits more than one oxidation number.
  • driers include inorganic or organic metal compounds, such as oxides, hydroxides, phosphates, carbonates, sulphates, sebacates, including neutral, acid or basic metal soaps. In terms of their metal content, the driers are used in a proportion ranging from 10 -3 to 4% by weight, relative to the binder solids content.
  • compositions of the invention are high-solids formulations and preferable have a solids content between about 70 and about 90% and more preferably between about 80 and about 90%.
  • the organic solvent is typically present at such an amount as to keep the volatile organic compound content below about 350 g/L, preferably below about 250 g/L and most preferable below 210 g/L.
  • the paint compositions according to the invention are particularly suitable for use as decorative paints. They can, be applied,in adequately high layer thickness and they have good hiding power and drying properties.
  • Carbohydrate esters of drying fatty acids, wherein the carbohydrate moiety is derived from oligomeric dextrines cannot be prepared by the methods described in this invention, but only by reaction of the carbohydrate with fatty acid chlorides or anhydrides (as described in WO 94/22919).
  • the fast drying binders thus obtained exhibit broader molecular weight distributions and much higher viscosity numbers than the inulin esters of the present invention with corresponding degrees of polymerisation.
  • esters of drying fatty esters with oligomeric dextrines, with a degree of substitution less than 2.5 are unsuitable as binder for alkyd paints, because they cannot be processed in the conventional way.
  • the molecular weight distribution was determined by Gel Permeation Chromatography (GPC apparatus from Millipore) using THF as solvent, 3 columns of Plgel 5mm, mixed-D from Polymer laboratories, calibration curve with commercial polystyrene standards.
  • the acid value was measured according to ASTM method D 1980-87 and the value is expressed in mg KOH/g
  • the hydroxyl value was measured according to ASTM method D 1957-86 and the value is expressed in mg KOH/g
  • the degree of substitution is the sucrose functionalities which are substituted; it was established by quantitative 13 C NMR, using a Bruker DPX 300 spectrometer.
  • the degree of polymerisation is number of monosaccharide units; it was determined by HPLC using a DIONEX unit.
  • the mixture was heated at a temperature of 70-75 °C under a stream of nitrogen. At that temperature 306 pbw of acetic anhydride was added. Heating was continued for an additional period of 4 hours. Then, after cooling, the volatiles were evaporated under reduced pressure (20 Pa). Thereupon traces of the remaining acetic acid were removed by codistillation under reduced pressure with consecutively toluene and ethanol. The resulting crude (containing about 20% of N,N-dimethylacetamide) product [inulin acetate with a degree of substitution (DS) of about 1.3] was used in the next step without further purification.
  • N,N-dimethylacetamide N,N-dimethylacetamide
  • the mixture was heated at a temperature of 140-142 °C under a stream of nitrogen for 8 hours. Then, the solvent was distilled off under reduce pressure (20 Pa). The residue thus obtained was dissolved in petroleum ether (boiling range: 40-60°C) and treated with one equivalent hydrogen peroxide (2 % aqueous solution; 1 mol per mol of monosaccharide unit) during one hour at a temperature of 25-30°C.
  • the resulting binder had the following properties:
  • the paint formulations were produced in the usual manner.
  • the coating ingredients were mixed, dispersed using a high-speed dissolver followed by pearl mill grinding. This formulation and the following paint compositions are described in Table 1. Properties of the paint have been established and are presented in Table 2.
  • the mixture was heated at a temperature of 70-75°C under a stream of nitrogen. At that temperature 55.1 pbw of acetic anhydride was added. Heating was continued for an additional period of 4 hours. Then, after cooling, the volatiles were evaporated under reduced pressure (20 Pa). Thereupon traces of the remaining acetic acid were removed by co-distillation under reduced pressure with consecutively toluene and ethanol. The resulting crude (containing about 20 % of N,N-dimethylacetamide) product [inuline acetate with a degree of substitution of about 0.9] was used in the next step without further purification.
  • the mixture was heated at a temperature of 140-142°C under a stream of nitrogen for 8 hours. Then, the solvent was distilled off under reduce pressure (20 Pa). The residue thus obtained was dissolved in petroleum ether (boiling range: 40-60°C) and treated with one equivalent hydrogen peroxide (2 % aqueous solution; 1 mol per mol of monosaccharide unit) during one hour at a temperature of 25-30°C.
  • the resulting binder had the following properties:
  • Paint based on Binder 2 was prepared as in example 1.
  • the paint composition is presented in Table 1. Properties of the paint have been established and are indicated in Table 2.
  • the mixture was heated at a temperature of 160-165°C under a stream of nitrogen. After 6 hours, the solvent and any remaining methanol were distilled under reduced pressure. The resulting product was dissolved in petroleum ether (boiling point: 40-60°C) and treated with one equivalent hydrogen peroxide (2 % aqueous solution; 1 mol per mol of monosaccharide unit) during 40 minutes at a temperature of 35°C.
  • the resulting binder had the following properties:
  • Paint based on Binder 3 was prepared as in example 1.
  • the paint composition is presented in Table 1. Properties of the paint have been established and are shown in Table 2.
  • the mixture was heated at a temperature of 160-165°C under a stream of nitrogen. After 6 hours, the solvent and any remaining methanol were distilled under reduced pressure (20 Pa). The resulting product was dissolved in petroleum ether (boiling point: 40-60°C) and treated with one equivalent hydrogen peroxide (2 % aqueous solution; 1 mol per mol of monosaccharide unit) during 40 minutes at a temperature of 35°C. After cooling to 25°C the organic layer was washed several times with methanol to remove the excess of safflower FAME.
  • the resulting binder had the following properties:
  • Paint based on Binder 4 was prepared as in example 1.
  • the paint composition is shown in Table 1. Properties of the paint have been established and are presented in Table 2.
  • the mixture was heated at a temperature of 160-165°C under a stream of nitrogen. After 6 hours, the solvent and any remaining methanol were distilled under reduced pressure (20 Pa). The resulting product was dissolved in petroleum ether (boiling point: 40-60°C) and treated with one equivalent hydrogen peroxide (2 % aqueous solution; 1 mol per mol of monosaccharide unit) during 40 minutes at a temperature of 35°C. After cooling to 25°C the organic layer was washed several times with methanol to remove the excess of safflower FAME.
  • the resulting binder had the following properties:
  • the resulting binder had the following properties:
  • Paint based on Binder 5 was prepared as in example 1.
  • the paint composition is shown in Table 1. Properties of the paint have been established and are presented in Table 2. Gloss retention upon QUV-A weathering was comparable to the performance of a commercial available gloss paint based on non-renewable materials, which was examined as comparative formulation. The gloss readings vs exposition time is demonstrated in Table 3.
  • the mixture was heated at a temperature of 160-165°C under a stream of nitrogen. After 6 hours, the solvent and any remaining methanol were distilled under reduced pressure (20 Pa). The resulting product was dissolved in petroleum ether (boiling point: 40-60°C) and treated with one equivalent hydrogen peroxide (2 % aqueous solution; 1 mol per mol of monosaccharide unit) during 40 minutes at a temperature of 35°C. After cooling to 25°C the organic layer was washed several times with methanol to remove the excess of safflower FAME.
  • the resulting binder had the following properties:
  • the resulting binder had the following properties:
  • Paint based on Binder 6 was prepared as in example 1.
  • the paint composition is shown in Table 1. Properties of the paint have been established and are presented in Table 2. Gloss retention upon QUV-A weathering was comparable to the performance of a commercial available gloss paint based on non-renewable materials, which was examined as comparative formulation. The gloss readings vs exposition time is demonstrated in Table 3.
  • the mixture was heated at a temperature of 160-165°C under a stream of nitrogen. After 6 hours, the solvent and any remaining methanol were distilled under reduced pressure (20 Pa). The resulting product was dissolved in petroleum ether (boiling point: 40-60°C) and treated with one equivalent hydrogen peroxide (2 % aqueous solution; 1 mol per mol of monosaccharide unit) during 40 minutes at a temperature of 35°C. After cooling to 25°C the organic layer was washed several times with methanol to remove the excess of safflower FAME.
  • the resulting binder had the following properties:
  • the resulting binder had the following properties:
  • Paint based on Binder 7 was prepared as in example 1.
  • the paint composition is shown in Table 1. Properties of the paint have been established and are presented in Table 2. Gloss retention upon QUV-A weathering was comparable to the performance of a commercial available gloss paint based on non-renewable materials, which was examined as comparative formulation.
  • Example 8 For comparison purposes, a dextrine linoleate ester was prepared.
  • binders according to the invention lacking aromatic backbone, display properties equivalent to the conventional and commercial high-solid alkyd paints.
  • drying fatty esters of dextrines as in example 8 could not be prepared by the methods according to the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Paints Or Removers (AREA)
  • Polyesters Or Polycarbonates (AREA)
EP03704483A 2002-01-30 2003-01-28 Polysaccharide esters and their use as binders in coatings Expired - Lifetime EP1470163B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03704483A EP1470163B1 (en) 2002-01-30 2003-01-28 Polysaccharide esters and their use as binders in coatings

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP02447016 2002-01-30
EP02447016 2002-01-30
EP03704483A EP1470163B1 (en) 2002-01-30 2003-01-28 Polysaccharide esters and their use as binders in coatings
PCT/EP2003/000845 WO2003064477A1 (en) 2002-01-30 2003-01-28 Polysaccharide esters and their use as binders in coatings

Publications (2)

Publication Number Publication Date
EP1470163A1 EP1470163A1 (en) 2004-10-27
EP1470163B1 true EP1470163B1 (en) 2005-12-28

Family

ID=27635941

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03704483A Expired - Lifetime EP1470163B1 (en) 2002-01-30 2003-01-28 Polysaccharide esters and their use as binders in coatings

Country Status (13)

Country Link
US (1) US20050215751A1 (da)
EP (1) EP1470163B1 (da)
CN (1) CN1642985A (da)
AT (1) ATE314398T1 (da)
CA (1) CA2474599A1 (da)
DE (1) DE60303010T2 (da)
DK (1) DK1470163T3 (da)
ES (1) ES2254905T3 (da)
IS (1) IS7363A (da)
PL (1) PL208103B1 (da)
RU (1) RU2004126248A (da)
WO (1) WO2003064477A1 (da)
ZA (1) ZA200406081B (da)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008085431A2 (en) * 2006-12-29 2008-07-17 The Sherwin-Williams Company Pretreatment and stain system
DE102007007738A1 (de) * 2007-02-09 2008-08-14 Südzucker AG Mannheim/Ochsenfurt Farbmarkierte Oligo- oder Polysaccharide
WO2010021856A2 (en) * 2008-08-18 2010-02-25 The Procter & Gamble Company Highly esterified polyol polyesters with one pair of conjugated double bonds
WO2010021857A1 (en) * 2008-08-18 2010-02-25 The Procter & Gamble Company Highly esterified polyol polyesters with two or more pairs of conjugated double bonds
US10167347B2 (en) * 2014-03-25 2019-01-01 Basf Se Carboxylate ester of polysaccharide

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1155879A (fr) * 1955-06-06 1958-05-09 Int Standard Electric Corp Système de communication électrique par impulsions
GB1399053A (en) * 1973-03-16 1975-06-25 Tate & Lyle Ltd Process for the production of surface active agents comprising sucrose esters
NL158165B (nl) * 1973-05-15 1978-10-16 Amsterdam Chem Comb Werkwijze voor de bereiding van carbonzuuresters van lineaire alifatische suikeralcoholen.
JP2811487B2 (ja) * 1989-12-27 1998-10-15 株式会社コーセー 油ゲル化剤及びこれを含有する化粧料
ES2121578T3 (es) * 1991-04-12 1998-12-01 Procter & Gamble Procedimiento para mejorar la estabilidad a la oxidacion de poliesteres de acido graso-polioles.
DE19607847C1 (de) * 1996-03-01 1997-11-20 Suedzucker Ag Aliphatische Carbonsäureester von Inulin
US5767257A (en) * 1996-07-19 1998-06-16 The Procter & Gamble Company Methods for producing polyol fatty acid polyesters using atmospheric or superatmospheric pressure
EP1066306B1 (en) * 1998-03-23 2003-05-21 The Procter & Gamble Company Synthesis of higher polyol fatty acid polyesters by transesterification
KR20010068972A (ko) * 2000-01-11 2001-07-23 한구재 메틸프룩토시드 올레산 폴리에스텔 및 그의 제조방법

Also Published As

Publication number Publication date
DE60303010D1 (de) 2006-02-02
WO2003064477B1 (en) 2003-12-18
PL208103B1 (pl) 2011-03-31
CA2474599A1 (en) 2003-08-07
WO2003064477A1 (en) 2003-08-07
RU2004126248A (ru) 2006-02-10
DE60303010T2 (de) 2006-08-24
DK1470163T3 (da) 2006-05-15
CN1642985A (zh) 2005-07-20
ZA200406081B (en) 2005-09-27
US20050215751A1 (en) 2005-09-29
PL372276A1 (en) 2005-07-11
EP1470163A1 (en) 2004-10-27
ES2254905T3 (es) 2006-06-16
IS7363A (is) 2004-07-22
ATE314398T1 (de) 2006-01-15

Similar Documents

Publication Publication Date Title
EP1470200B1 (en) Reactive diluents and coatings comprising them
EP1778751B1 (en) Carbohydrate based alkyds
ZA200406081B (en) Polysaccharide esters and their use as binders in coatings.
CN104271634A (zh) 树脂、组合物和用途
CN114133541B (zh) 一种高耐水解聚酯多元醇及其制备方法和在水性聚氨酯树脂中的应用
EP1554349A1 (en) Air drying waterborne resin composition
AU2003206791A1 (en) Polysaccharide esters and their use as binders in coatings
Domenek et al. Bacterial polyesters grafted with poly (ethylene glycol): behaviour in aqueous media
EP1470178B1 (en) Air-drying paint compositions comprising carbohydrate-based polyesters
CA2689564C (en) Polysiloxane and urethane modified water-reducible alkyd resins
AU2003205693A1 (en) Air-drying paint compositions comprising carbohydrate-based polyesters
AU2003218640A1 (en) Reactive diluents and coatings comprising them
EP3856746B1 (en) Cyclic ether- and hydroxyl-containing compositions useful for producing fast dry alkyd polymers and methods for making such cyclic ether- and hydroxyl-containing compositions
van Haveren et al. Towards sustainability. Alkyd resins and alkyd drying agents based on renewable resources
WO2010021857A1 (en) Highly esterified polyol polyesters with two or more pairs of conjugated double bonds
Akintayo Synthesis and characterization of acrylated Parkia biglobosa medium oil alkyds
WO2018029312A1 (en) Combination of reactive diluents

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040813

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO

17Q First examination report despatched

Effective date: 20050209

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051228

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051228

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051228

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051228

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051228

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060131

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060131

REF Corresponds to:

Ref document number: 60303010

Country of ref document: DE

Date of ref document: 20060202

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060328

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060328

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060328

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060529

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2254905

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E000346

Country of ref document: HU

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

ET Fr: translation filed
REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20060929

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051228

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20160120

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SK

Payment date: 20160127

Year of fee payment: 14

Ref country code: IT

Payment date: 20160127

Year of fee payment: 14

Ref country code: CZ

Payment date: 20160126

Year of fee payment: 14

Ref country code: DK

Payment date: 20160120

Year of fee payment: 14

Ref country code: ES

Payment date: 20160112

Year of fee payment: 14

Ref country code: DE

Payment date: 20160120

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20160120

Year of fee payment: 14

Ref country code: FR

Payment date: 20160121

Year of fee payment: 14

Ref country code: GB

Payment date: 20160120

Year of fee payment: 14

Ref country code: HU

Payment date: 20160120

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170131

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60303010

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20170131

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20170201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20170128

REG Reference to a national code

Ref country code: SK

Ref legal event code: MM4A

Ref document number: E 601

Country of ref document: SK

Effective date: 20170128

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20170929

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170128

Ref country code: SK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170128

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170201

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170801

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170128

Ref country code: HU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170131

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20170131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170128

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170129

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20181113